Acid sulphuric acid ester compound of aromatic hydroxyalkylethers



Patented Get. 4, 1927:-

"UNITED STATES 1,644,524 PATENT OFFICE.

YORK, N. Y., A. oonro'm'rron or DELAWARE. I a

wmrmn HENTRICH AND mnx-nnnn'rmnumor wIEsDoRE, NEAR coLoGNn-oN-mm- RHINE,GERMANY, nssreuons T GRASSELLI DYESTUFF ooitronnrron, on NEW ACIDSULPHURIC ACID ESTER COMPOUND OF AROMA'IIC H YDROXYALKYLETZQIERS.

No Drawing. App1ication filed June 21, 1926. Serial No. 117,595, and inGermany June 25; 1.923.

Our invention resides in novel acid sul- I phuric acid ester compoundsof aromatic hy-' I droxyalkylethers a19in processes of making the same.

The compounds may be generally designated'by the formula: IaryLO-alkyl-O-SO OX in which X stands for hydrogen or a forming basicresidue.

We have found that by sulphating aromatic hydroxyalkylethers of thegeneral formula aryl-O-alkyl-OH at temperatures below 100 .C. the freehysalt droxylgroup attached to the alkylgroup is esterified andacid'sulphuricacid esters are formed to which the general formulacalcium salts, separation-from the precipitat- I ed calcium sulphate andtransposition with alkali metal salts. v

The alkali metal salts of the acid esters are easily water soluble,usually crystalline substances, and differ only slightly in theirproperties from the free acid esters. 1

tained from them are usually distinguished x y 4 by improvedsolubilityand increased aifinity.

' naphtholates or hydroxyanthracene alkali The alkali metal salts of theacid esters maybe generally designated by the formula: aryl-O-alkyl-O sO-O-alkali metal These novel sulphuric acid ester comyestuffintermediates; the dyestufis ob.-

for artificial silk and kindred products.

Many of the hydroxyalkylethers from which our novel sulphuric acidestersare derived have v:notbeen prepared heretofore. They are easily obtainedby reacting-with halohydrines upon alkali metal phenolates,

metal salts.

ounds are mainly intended to be" used as trate our invention, itbeing'understood that our inventlon Is not limited to the particularsubstances mentioned, norto the specific The following examples ,willfurther conditions used therein. The parts are by Weight.

Example 1.-15 parts 3-nitro-4-hydrox y-1:

.methylbenzene are. dissolved in 50 parts wa ter containing 4 partscaustic soda. To this -8'parts glycol chlorhydrin are added and thereaction mass boiled at reflux for several hours.- An Oll separateswhich is stirred up ith sodium carbonate solution,i.allowed to settleand dried; it solidifies to yellowishwhite crystals, melting at 40 C.and is the ether of the formula Y No,

10 parts of this novel 3-nitro-1-methylbenaenel-ethylene-glycol etherare introduced into 30 parts sulphuric acid 66 B. temperaturerises toabout 50 C. and the sulphation sets in and is finished in a short time;The reaction mass is then poured into ice water and the clear solutionsalted out with potassium chloride. The potassium salt of the acidsulphuric acid ester of 3-nitromethylbenzene-4-ethylene-glycol etherseparates as yellowish-white crystals. It is exceedinglysoluble in Waterand has most probably the formula I Hw-Go-CE-CHEO-SOi-OK I The alkalimetal salts generally may be designated by the formula:.

- no, cm-Go-tilflm-o-sm-o-mmu metal 7 The nitro group of this'ester'canbe reduced to the amino group and the so obtained-- amine diazotized;Bycouplirig thimdiazo compound with beta naphthol a solublelbluish-reddyestutf-and with -nitroaniline a red dyestufl is obtained which isparticularly suited for dyeing'cellulose acetate silk.

Example 2.- 5 parts beta-naphth l-ethyleneglycol described in theChemise es Zen- Thetral-Blatt 1914,11, pages 1307 and 130s and which hasthe formula is dissolved in 15 parts 66 B. sul huric acid. Thetemperature rises to 7 0 and the sulphation is completedin a fewminutes. The react-ion massis poured into ice water and the solutionsaturated under stirring with sodium chloride. The sodium salt of theacid sulphuric acid ester of beta-naphthyl-ethylene-gl col etherseparates asbrilliant white lea ets. ,It has most probably the formula a(no-onr-cm-so-so -om V Example 3. -'-Alpha'- anthranyl-ethyleneglycolether of the formula OCHg-CHr-OH which can be obtained from alha-hydroxy anthraceneand glycol-chlorhy rin is, when recrystallized fromalcohol, grayish-brown 1 crystals of a melting point of 117 1l8 0.

-l0 parts of this ether are introduced into 30 parts 66 B. sulphuricacid, keeping the temperature below 15. C. After complete solution isobtained the mass is poured-into 200 parts ice water and 30 parts commonsalt added. The sodium salt of the acid" sulphuric acid esterofalpha-anthranylethyleneglycol ether separates. .It is, aftert'lrying,-a grayish-black powder, easily soluble in water with a browncolor and has. most probably the formula Example .4, 10 parts ofalpha-naphthylalpha-betwgamma "trihydroxyp'ropane de scribed inGhemisches Zentralblatt, 1908, II, page 2011 and having the formula I0-cm-cn-cm-on are introduced with cooling into25 p artssfifi B.sulphuric acid, keepin the temperature below 25 C. After the so ution iscomplete i1 it is poured into 200 parts water and a clear solution isobtained. This is neutralized with calcium carbonate'and filtered fromthe precipitated calcium sulphate. The filtrate contains the calciumsalt of the acid sulphuricacid ester of alpha-naphthyltrihydroxypropane. The requisite amount of soda ash is now added,filtered from calcium carbonate and the filtrate evaporated to dryness.A viscous, easily water-soluble mass is obtained which is the sodiumsalt of the acid ester of the formula o-cm-cH-cm-o-soy-om We claim 1. Inprocesses of making-acid sulphuric acid ester compounds of aromatichydroxyalkyl ethers the step comprising treating aromatic hydroXy-alkylethers with'sulphating agents at room temperatures. 2. In processes ofmaking acid sulphuric acid ester compounds of aromatichydroxyaryl-O-alkyl-O-SOQOX in which X stands for hydrogen or a salttormlng-basic residue, which are water so1uble substances.

' As new products alkali metal salts of acid sulphuric acid estersofaromatic hy-v droxy-alkyl ethers of the probable general i'ormulaaryl-O-alkyl-O-SO -O-alkali metal which are water soluble substances, Y6. As a new product the alkali metal salts of the acid sulphuric acidester of 3-nitromethylbenzene-4-ethyleneglycol ether having mostprobably the formula In testimony whereof, we afiix our signatures. s

' WINFRI'D iaENTRIoH.

. MAXHA'RDTMANN.

